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The bending vibrational levels of the acetylene cation: a case study of the Renner-Teller effect in a molecule with two degenerate bending vibrations
Forty three vibronic levels of C2H2+, X 2Pi u, with upsilon4 = 0-6, upsilon5 = 0-3, and K = 0-4, lying at energies of 0-3520 cm(-1) above the zero-point level, have been recorded at rotational resolution. These levels were observed by double resonance, using 1+1' two-color pulsed-field ionizati...
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Published in: | The Journal of chemical physics 2006-10, Vol.125 (13), p.133201-133201 |
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Main Authors: | , , , |
Format: | Article |
Language: | English |
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Online Access: | Get full text |
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Summary: | Forty three vibronic levels of C2H2+, X 2Pi u, with upsilon4 = 0-6, upsilon5 = 0-3, and K = 0-4, lying at energies of 0-3520 cm(-1) above the zero-point level, have been recorded at rotational resolution. These levels were observed by double resonance, using 1+1' two-color pulsed-field ionization zero-kinetic-energy photoelectron spectroscopy. The intermediate states were single rovibrational levels chosen from the A1Au, 4nu3 (K = 1-2), 5nu3 (K = 1), nu2+4nu3 (K = 0), and 47,206 cm(-1) (K = 1) levels of C2H2. Seven of the trans-bending levels of C2H2+ (upsilon4 = 0-3, K = 0-2) had been reported previously by Pratt et al. [J. Chem. Phys. 99, 6233 (1993)]; our results for these levels agree well with theirs. A full analysis has been carried out, including the Renner-Teller effect and the vibrational anharmonicity for both the trans- and cis-bending vibrations. The rotational structure of the lowest 16 vibronic levels (consisting of the complete set of levels with upsilon4 + upsilon5 < or = 2, except for the unobserved upper (2Pi u component of the 2nu4 overtone) could be fitted by least squares using 16 parameters to give an rms deviation of 0.21 cm(-1). The vibronic coupling parameter epsilon5 (about whose magnitude there has been controversy) was determined to be -0.0273(7). For the higher vibronic levels, an additional parameter, r45, was needed to allow for the Darling-Dennison resonance between the two bending manifolds. Almost all the observed levels of the upsilon4 + upsilon5 = 3 and 4 polyads (about half of the predicted number) could then be assigned. In a final fit to 39 vibronic levels with upsilon4 + upsilon5 < or = 5, an rms deviation of 0.34 cm(-1) was obtained using 20 parameters. An interesting finding is that Hund's spin-coupling cases (a) and (b) both occur in the Sigmau components of the nu4 + 2nu5 combination level. The ionization potential of C2H2 (from the lowest rotational level of the ground state to the lowest rotational level of the cation) is found to be 91,953.77 +/- 0.09 cm(-1) (3sigma). |
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ISSN: | 0021-9606 1089-7690 |
DOI: | 10.1063/1.2199827 |